Process for the production of phosphor organic compounds

ABSTRACT

A novel process is described for preparing phosphonites or phosphinites by reacting a product of a Friedel-Crafts reaction with alcohols or phenols and separating off the byproducts formed. The novelty is the aftertreatment with a protic compound, or with an oxide, hydroxide, (hydrogen)carbonate resp. (hydrogen)phosphate of a metal or with a nitrogen containing compound (as defined in claim  1 ), or with any combination of one or more substances of the above mentioned compound classes. Products having a low halide and aluminium content are obtained which are distinguished by an improved clear solubility and an improved action as stabilizer for polymeric materials.

This Appn is a con of U.S. application Ser. No. 09/508,623 filed Mar.10, 2000 which is a 371 of PCT/IB99/01479 Aug. 27, 1999

FIELD OF THE INVENTION

The invention relates to a process for preparing phosphonites orphosphinites, in particular aromatic phosphonites or phosphinites,having significantly improved properties for stabilizing polymermaterials. Products made by this process of the invention aredistinguished by higher activity, improved hydrolysis stability andclear solubility as well as a markedly decreased content of unwantedbyproducts.

BACKGROUND OF THE INVENTION

As known to those skilled in the art, aromatic phosphonites orphosphinites may be prepared by Friedel-Crafts reaction (reaction 1) ofaromatics with halogen-containing phosphorous compounds such asphosphorus trichloride, phosphorus tribromide resp. alkyl- oraryidihalophosphines. The aluminium halide adducts initially formed arecleaved by recomplexing with tertiary amines or phosphoryl chloride bymethods known from the literature (reaction 1a). In a subsequentreaction (reaction 2) of the resultant aryldihalophosphines,alkylarylhalophosphines or diarylhalophosphines with alcohols or phenolsin the presence or absence of inert solvents and/or acid-binding agentssuch as tertiary amines, for example, the desired phosphonites orphosphinites are obtained. In this case “halogen” is chloride orbromide, but preferably chloride. These reaction paths have long beenknown and are described in the literature (e.g. Michaelis, Ann., 293,193 (1896); Kosolapoff, G. M., Organic Phosphorus Compounds, John Wiley& Sons, New York, 1972). The reaction diagrams below also explicitlyinclude a multiplicity of reactions of types 1 and 2 on one aromaticsubstrate, e.g. the Friedel-Crafts reaction of diphenyl with 2equivalents of phosphorus trichloride. The individual reaction partnerscan be used in this case in a deficiency, stoichiometrically or inexcess amounts. Reactions of this type are described, for example, in GBPatent 1372528.

Reaction 1

Reaction 1a

Reaction 2

a) in the presence of an acid acceptor:

b) without use of an acid acceptor:

where independently of one another, each group

R is an aliphatic, cycloaliphatic or aromatic organic radical having1-36 carbon atoms, which can also contain hetero atoms (N, O, P, S)

R′ is Hal or R;

R″ is an aliphatic, cycloaliphatic or aromatic organic radical having1-36 carbon atoms, which can also contain hetero atoms (N, O, P, S);

R′″ is an aliphatic, cycloaliphatic or aromatic organic radical having1-36 carbon atoms, which can also contain hetero atoms (N, O, P, S), orN(R′″)₃ as such is pyridine or alkyl-substituted pyridine;

Hal is Cl or Br

n is 0-5

m is equal to 1 if R′=R and m is equal to 2 if R′=Hal.

The said reaction mixtures may, under some circumstances, also furthercomprise organic or organophosphorus compounds such as phenols,alcohols, amines or phosphites, phosphonates, phosphates etc. which arelikewise formed during the phosphonite/phosphinite synthesis, remain inthe mixture as excess at the end of the reaction or else aredeliberately added.

The reaction of Friedel-Crafts reaction products with alcohols orphenols to form phosphonites or phosphinites takes place either withoutsolvent, in the presence of an inert non-polar solvent (such asaliphatics, cycloaliphatics or mixtures thereof), or alternativelywithout, with stoichiometric or superstoichiometric amounts of an acidacceptor (see reaction 2a).

Common to all these preparation processes is the fact that a certainproportion of unwanted byproducts is present, which byproducts result,for example, from the incomplete reaction of the halophosphoruscompounds or are due to residual small amounts of aluminium halide oramine hydrohalide salts. According to the classical procedure, thesemust be removed by complex and cost-intensive purification processes,such as crystallization, distillation, filtration processes or membraneprocesses or ion exchange, if a pure product is to be obtained. If thesebyproduct salts remain in the product, its properties and the usabilityas polymer stabilizer may be impaired. Thus, the clear solubility,particularly in nonpolar solvents, or else the transparency of thepolymers, is decreased, an increase in the corrosivity to metals,promoted by halide ions, can occur and unwanted decomposition processes,such as the hydrolysis of the compounds themselves or of hydrolysablepolymers such as polyester or polycarbonate can also be promoted.

SUMMARY OF THE INVENTION

The object of the invention is to decrease significantly the content ofunwanted byproducts in a simple and cost-effective manner and at thesame time to increase the amount of active substance.

It has surprisingly been found that, after the preparation as describedabove of the reaction mixtures comprising phosphonites and/orphosphinites, the addition of a small amount of one or more proticcompounds such as alcohols, ammonia, primary or secondary amines orwater alone or, preferably, in combination with an oxide, hydroxide,(hydrogen)carbonate or (hydrogen)phosphate of a metal and subsequentsimple separation of only a small amount of solids after a suitablereaction time leads to a significant decrease in the halide contents, animprovement in the clear solubility in nonpolar solvents, a decrease inthe aluminium content and an improved action as stabilizer for polymermaterials compared with a phosphonite/phosphinite according to the priorart.

Alternatively, a small amount of one or more nitrogen containingsubstances of the group consisting of carbonic acid amides, thiocarbonicacid amides, carbonic acid imides, thiocarbonic acid imides, lactames,thiolactames, carbonic acid hydrazides, urea, thiourea, symmetricallyand asymmetrically substituted urea and thiourea derivatives, urethanes,uretimides as well as guanidine and its salts or melamine andderivatives thereof, including polymeric compounds of all named classes,or an oxide, hydroxide, (hydrogen)carbonate or (hydrogen)phosphate of ametal may be used alone or, preferably, in combination with a proticcompound as defined above and leads to a similar result as describedabove.

Furthermore, combinations of one or more protic compounds and/or of oneor more nitrogen containing substances (all as defined above) with anoxide, hydroxide, (hydrogen)carbonate or (hydrogen)phosphate of a metalcan be used to improve the properties of phosphonites/phosphinites asdescribed above.

DETAILED DESCRIPTION OF THE INVENTION

The invention therefore relates to a process for preparing phosphonitesor phosphinites of the general formula (I)

where

aryl is a substituted or unsubstituted aryl or heteroaryl radical;

R is any organic radical having 1-36 carbon atoms, which can alsocontain hetero atoms; and

A is either R or OR,

by reacting a product of a Friedel-Crafts reaction of the generalformula (II)

where

aryl has the meaning above;

Hal is halogen; and

A′ is either Hal or R,

with a compound of the general formula (III)

R—OH  (III)

where R has the meaning above, and separating off the byproducts formed,characterized in that an aftertreatment is carried out with a proticcompound such as alcohols, ammonia, primary or secondary amines orwater, or with an oxide, hydroxide, (hydrogen)carbonate or(hydrogen)phosphate of a metal, or with a nitrogen containing compoundof the group consisting of carbonic acid amides, thiocarbonic acidamides, carbonic acid imides, thiocarbonic acid imides, lactames,thiolactames, carbonic acid hydrazides, urea, thiourea, symmetricallyand asymmetrically substituted urea and thiourea derivatives, urethanes,uretimides as well as guanidine and its salts or melamine andderivatives thereof, including polymeric compounds of all named classes,or in any combination of one or more substances of the above mentionedcompound classes, in the absence of solvent or in an inert, nonpolarsolvent and the resultant byproducts are again separated off.

The reaction with the agents of the invention takes place either in theabsence of solvent or in inert, nonpolar solvents such as alkanes oraromatics (e.g. benzene, toluene, xylenes, pyridine) or their mixtures,but particularly preferably in alkanes (e.g. heptane, cyclohexane,isooctane, decalin), alkane mixtures (e.g. boiling-point fractions ofpetroleum ethers) or technical-grade alkane mixtures having only a lowcontent of aromatics. The previously preferred use of chloroaromatics,such as chlorobenzene or dichlorobenzene, as solvent can be avoided bythe process described.

The described procedure gives considerable simplifications in theremoval of the byproducts, since these, together with the auxiliaryagents, are produced only in small amounts and in readily removableform.

Preferably, agent mixtures of alcohols or water together with oxides,hydroxides or carbonates of alkali and alkaline earth metals and of zincor with a nitrogen containing compound are used in the workup ofphosphonites/phosphinites, in which case other compounds such asphosphites, phenols and amines can also be present.

Particular preference is given to the use of mixtures of water andoxides or hydroxides of the alkali and alkaline earth metals or anitrogen containing compound, selected from the group of carbonic acidamides, imides, lactames, urea, thiourea, substituted urea, melamine andits derivatives as well as polymeric compounds of all these classes, inthe workup of aromatic phosphonites/phosphinites, in which case othercompounds such as phosphites, phenols and amines can also be present.

Very particular preference is given to the use of mixtures of water andoxides of magnesium or calcium and also hydroxides of sodium, potassium,magnesium and calcium or carbonic acid amides, urea or melamine in theworkup of aromatic phosphonites/phosphinites in the presence ofcompounds such as phosphites, phenols and amines.

The amounts used are 0.1-50 mol % of the protic compound, with respectto the amount of phosphonite/phosphinite, and 0.1-50 mol % of theoxides, hydroxides, (hydrogen)carbonates or phosphates of a metal or ofthe nitrogen containing compound.

Preferred amounts are 0.5-35 mol % of the protic compound, with respectto the amount of phosphonite/phosphinite, and 0.5-35 mol % of theoxides, hydroxides, (hydrogen)carbonates or phosphates of metals of maingroups I, II and III of the Periodic Table of the Elements and of zincor of the nitrogen containing compound.

Particularly preferred amounts are 1-25 mol % of the protic compound,with respect to the amount of phosphonite/phosphinite, and 1-25 mol % ofthe oxides or hydroxides of metals of main groups I and II of thePeriodic Table of the Elements or 5-30 mol % of the nitrogen containingcompound.

The invention is especially suitable for working up a reaction mixturebased on the reaction product of 2,4-di-tert-butylphenol with theFriedel-Crafts reaction product of diphenyl and phosphorus trichloride(cf. in this context Chemical Abstracts Number [119345-01-6]; trade nameSandostab® P-EPQ®).

A further possibility consists in the aftertreatment with a combinationof a nitrogen containing compound, a protic compound and an oxide,hydroxide, (hydrogen)carbonate or (hydrogen)phosphate of a metal.Preferred compounds are those of alkali and earth alkali metals andzinc. The amounts of such combination to be used are 0.1-50 mol %,preferably 0.5-35 mol %, most preferably 1-25 mol % with respect to theamount of phosphonite/phosphinite.

The phosphonites or phosphinites obtained by the process of theinvention are distinguished by a significant lowering of the halidecontents, an improvement in the clear solubility in nonpolar solvents, adecrease in the aluminium content and an improved action as stabilizerfor polymer materials. Compared with phosphonites or phosphinites of theprior art, which have a content of chloride or hydrolysable chlorine ofat least 0.8%, determined by argentometric titration, the phosphonitesor phosphinites of the invention have a content of less than 0.5%, inthe particularly pure form, of less than 0.3%. The aluminium content,determined by the AES/ICP (atomic emission spectroscopy/inductivelycoupled plasma) method, is in each case at least 800 ppm or less than500 ppm, respectively. The clear solubility in nonpolar solvents can bemeasured by means of turbidity in a 10% strength solution in isooctane.

The resultant phosphonites or phosphinites which are improved in theirproperties, or their mixtures with other compounds already mentionedabove, may be used for stabilizing polymer materials. Polymer materialswhich may be mentioned are as follows:

1. Polymers of mono- and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene and polymers of cycloolefins such as cyclopentene ornorbornene; in addition polyethylene (which may optionally becrosslinked), e.g. high-density polyethylene (HDPE), low-densitypolyethylene (LDPE), linear low-density polyethylene (LLDPE), branchedlow-density polyethylene (BLDPE). Polyolefins, i.e. polymers ofmonoolefins, in particular polyethylene and polypropylene, can beprepared by various processes, especially by the following methods:

a) free-radical (usually at high pressure and high temperature).

b) by means of a catalyst, where the catalyst usually comprises one ormore metals of groups IVb, Vb, VIb or VIII. These metals usually haveone or more ligands such as oxides, halides, alkoxides, esters, ethers,amines, alkyls, alkenyls and/or aryls, which can be either -π- orα-coordinated. These metal complexes can be free or fixed to supports,such as on activated magnesium chloride, titanium chloride, aluminiumoxide or silicon oxide. These catalysts can be soluble or insoluble inthe polymerization medium. The catalysts can be active as such in thepolymerization, or other activators can be used, for example metalalkyls, metal hydrides, metal alkylhalides, metal alkyloxides or metalalkyloxanes, the metals being elements of Groups Ia, IIa and/or IIIa.The activators can be modified, for example, with further ester, ether,amine or silyl ether groups. These catalyst systems are usually termedPhillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of mono- and diolefins with one another or with othervinyl monomers, for example ethylene-propylene copolymers, linearlow-density polyethylene (LLDPE) and mixtures thereof with low-densitypolyethylene (LDPE), propylene-but-1-ene copolymers,propylene-isobutylene copolymers, ethylene-but-1-ene copolymers,ethylene-hexene copolymers, ethylene-methylpentene copolymers,ethylene-heptene copolymers, ethylene-octene copolymers,propylene-butadiene copolymers, iso-butylene and isoprene copolymers,ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylatecopolymers, ethylene-vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene-acrylic acid copolymers and their salts(ionomers), as well as terpolymers of ethylene with propylene and adiene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; inaddition mixtures of such copolymers with one another and with polymersmentioned under 1), for example polypropylene/ethylene-propylenecopolymers, LDPE-ethylene-vinyl acetate copolymers,LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinyl acetatecopolymers, LLDPE/ethylene-acrylic acid copolymers and alternating orrandom polyalkylene-carbon monoxide copolymers and mixtures thereof withother polymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifier resins) and mixtures ofpolyalkylenes and starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of stynene or α-methylstyrene with dienes or acrylicderivatives, for example styrene-butadiene, styrene-acrylonitrile,styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate,styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride,styrene-acrylonitrile-methylacrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene-propylene-diene terpolymer; and blockcopolymers of styrene, such as styrene-butadiene-styrene,styrene-isoprene-styrene, styrene-ethylene/butylene-styrene orstyrene-ethylene/propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylon-itrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, styrene andacrylonitrile on ethylene-propylene-diene terpolymers. Styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate-butadiene copolymers, as well as mixturesthereof with the copolymers mentioned under 6), for example as known asABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers, such as polychloroprene, chlorinatedrubber, chlorinated or sulphochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride; as well as copolymers thereof such as vinylchloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidenechloride-vinyl acetate.

9. Polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates and polymethacrylates, polymethyl methacrylates,polyacrylamides and polyacrylonitriles impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with one another orwith other unsaturated monomers, for example acrylonitrile-butadienecopolymers, acrylonitrile-alkyl acrylate copolymers,acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinylhalide copolymers or acrylonitrile-alkyl methacrylate-butadieneterpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, such as polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in section 1.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain comonomers, for example ethylene oxide; polyacetalsmodified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and polyphenylene sulphides, and mixturesthereof with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters and polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as nylon 4, nylon 6, nylon 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, nylon11 and nylon 12, aromatic polyamides starting from m-xylene, diamine andadipic acid; polyamides prepared from hexamethylenediamine andisophthalic and/or terephthalic acid and with or without an elastomer asmodifier, for example poly-2,4,4-trimethylhexamethylene terephthalamideor poly-m-phenylene isophthalamide, block copolymers of theaforementioned polyamides with polyolefins, olefin copolymers, ionomersor chemically bonded or grafted elastomers; or with polyethers, e.g.with polyethylene glycol, polypropylene glycol or polytetramethyleneglycol. In addition, polyamides or copolyamides modified with EPDM orABS, and polyamides condensed during processing (“RIM polyamidesystems”).

17. Polyureas, polyimides, polyamide-imides, and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and dialcohols and/orfrom hydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polylbutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, poly-hydroxybenzoates, aswell as block polyether esters derived from hydroxyl-terminatedpolyethers; in addition, polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulphones, polyether sulphones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, urea or melamine on the other hand, such as phenol-formaldehyderesins, urea-formaldehyde resins and melamine-formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containinglow-flammability modifications thereof.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample from epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanals or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombis-glycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, natural rubber, gelatin andderivatives thereof which have been chemically modified in apolymer-homologous manner, for example cellulose acetates, cellulosepropionates and cellulose butyrates, or the cellulose ethers such asmethyl cellulose; as well as rosins and derivatives.

28. Mixtures (polyblends) of the aforementioned polymers, for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Natural and synthetic organic substances which constitute puremonomeric compounds or mixtures thereof, for example mineral oils,animal or vegetable fats, oils and waxes, or oils, waxes and fats basedon synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates), and also blends of synthetic esters with mineral oils inany desired proportion by weight, as are employed, for example, as spinfinishes, and aqueous emulsions thereof.

30. Aqueous emulsions of natural or synthetic rubbers, such as naturalrubber latex or latices of carboxylated styrene-butadiene copolymers.

In these polymers, further additives may be present, for example:

1. Antioxidants

1.1 Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol,2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-buytl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-meth-oxymethylphenol, 2,6-dinonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl) phenol,2,4-dimethyl-6-(1′-methylheptadecyl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2 Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecyl-thiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-di-phenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl--4-hydroxy-anisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-lert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5 Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulphic.

1.6 Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylene-bis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidene-bis(4,6-di-tert-butylphenol),2.2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methy-lenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-bulyl-1-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl-mercaptobutane,ethylene glycol bis[3,3-bis′(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis(3,5-di-methyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl4-hydroxy-2-methylphenyl)pentane.

1.7 O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3.5-dimethylbenzyl mercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulphide, isooctyl3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8 Hydroxybenzylated malonates, for example dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydrorybenzyl)malonate, dioctadecyl2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl4-hydroxybenzyl)malonate,di[4-(1,1,3,3-tetramethylbutyl)phenyl],2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malo-nate.

1.9 Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-buty)-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-buryl-4-hydroxybenzyl)phenol.

1.10 Triazine compounds, for example2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octyl-mercapto4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11 Benzylphosphonates, for example dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl5-tert-butyl-4-hydroxy-3-methyl-benzylphosphonate, the Ca salt of themonoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12 Acylaminophenols, 4-hydroxylauramide, 4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13 Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethyl-hexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.14 Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabi-cyclo[2.2.2]octane.

1.15 Esters of β-(3,5-dicyclohexyl-4-hydroxy-phenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3 thiaundecanol,3-thiapentadecanol, trimethyl-hexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.16 Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N-bis-(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethyl-hexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.17 Amides of β-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid,e.g.N,N′-bis(3,5-di-tert-butyl4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpro-pionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine.

2. UV Absorbers and Light Stabilizers

2.1 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole.2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1.3,3-tetramethylbutyl)phenyl)benzo-triazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3-tert-butyl-2′- hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxy-phenyl)benzotriazole,2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl-2′-hydroxyphenyl)benzotriazole, amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbony-lethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonyl-ethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)-phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxy-phenyl)benzotriazole,2-(3′-dodecyl2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenyl-benzotriazole,2,2′-methy-lene-bis[4(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of2-[3-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxy-phenyl]benzotriazolewith polyethylene glycol 300, [R—CH₂CH₂—COO(CH₂)₃]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

2.2 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-dimethoxy derivative.

2.3 Esters of substituted or unsubstituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butyl-phenyl3,5-di-tert-butyl-4-hydroxy-benzoate.

2.4 Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate orisooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxycinnamate or butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbo-methoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5 Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6 Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperidyl) sebacate,bis(2,2,6,6-tetramethylpiperidyl) succinate,bis(1,2,2,6,6-pentamethylpiperidyl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonate, the condensationproduct of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine andsuccinic acid, the condensation product ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetraoate,1,1′-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-penta-methylpiperidyl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]de-cane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, thecondensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensation product of2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane, the condensation product of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethyl-piperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triaz-aspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetra-methyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperi-dyl)pyrrol-idine-2,5-dione.

2.7 Oxalamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,2,2′-didodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of o- andp-methoxy-disubstituted and of o- and p-ethoxy-disubstituted oxanilides.

2.8 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxy-phenyl)-4,6-bis(2;4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hy-droxy-3-butyloxytpropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hy-droxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example, N,N′-diphenyloxalamide,N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyl-oylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butyl-phenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythri-tol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bisisodecyloxy pentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite,bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

5. Peroxide scavengers, examples being esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl ester,mecaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulphide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

6. Polyamide stabilizers, examples being copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

7. Basic costabilizers, examples being melamin, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example Castearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, Kpalmitate, antimony pyrocatecholate or tin pyrocatecholate.

8. Nucleating agents, such as benzoic acid, 4-tert-butylbenzoic acid,adipic acid; diphenylacetic acid and their salts, phosphates,phosphonates and phosphinates and their esters and salts or clarifiers,such as derivatives of di-benzylidene sorbitol.

9. Fillers and reinforcing agents, examples being calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulphate,metal oxides and hydroxides, carbon black, graphite.

10. Other additives, examples being plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,antistatics, blowing agents.

These additional additives can be added to the polymers before, togetherwith or after addition of the stabilizers of the invention. Theseadditives and also the stabilizers of the invention can be added in thiscase as solid, in solution or melt as well as in the form of solid orliquid mixtures or masterbatches/concentrates.

The advantageous action of the compounds prepared according to theinvention is to be shown by the examples below, but the applicability tosimilar areas is not to be restricted by this.

EXAMPLES PREPARATION EXAMPLE 1 (PRODUCT 1)

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert-butylphenol, 102 ml of pyridine in220 ml of isooctane. After a reaction time of 2 h at approximately 85°C., 220 ml of isooctane are added to separate off the aluminium complexformed and the resulting product solution is admixed with 0.026 mol ofcalcium oxide and 0.026 mol of water. The mixture is stirred for 1 h andthe solid present is filtered off at room temperature. After taking offthe solvent in vacuum, a melt remains which, after it is poured out,solidifies as a pale-yellowish transparent glass.

PREPARATION EXAMPLE 2 (PRODUCT 2)

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert-butylphenol, 102 ml of pyridine in220 ml of isooctane. After a reaction time of 2 h at approximately 85°C., 220 ml of isooctane are added to separate off the aluminium complexformed and the resulting product solution is admixed with 0.032 mol ofcalcium hydroxide and 0.032 mol of water. The mixture is stirred for 1 hand the solid present is filtered off at room temperature. After takingoff the solvent in vacuum, a melt remains which, after it is poured out,solidifies as a pale-yellowish transparent glass.

PREPARATION EXAMPLE 3 (PRODUCT 3)

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert-butylphenol, 102 ml of pyridine in220 ml of isooctane. After a reaction time of 2 h at approximately 85°C., 220 ml of isooctane are added to separate off the aluminium complexformed and the resulting product solution is admixed with 0.016 mol ofcalcium oxide and 0.016 mol of sodium hydroxide solution (30% byweight). The mixture is stirred for 1 h and the solid present isfilteredd off at room temperature. After taking off the solvent invacuum, a melt remains which, after it is poured out, solidifies as apale-yellowish transparent glass.

PREPARATION EXAMPLE 4 (PRODUCT 4)

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert-butylphenol, 102 ml of pyridine in220 ml of isooctane. After a reaction time of 2 h at approximately 85°C., 220 ml of isooctane are added to separate off the aluminium complexformed and the resulting product solution is admixed with 0.016 mol ofsodium hydroxide solution (30% by weight). The mixture is stirred for 1h and the solid present is filtered off at room temperature. Aftertaking off the solvent in vacuum, a melt remains which, after it ispoured out, solidifies as a pale-yellowish transparent glass.

PREPARATION EXAMPLE 5

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert.butylphenol, 102 ml pyridine in 220ml iso-octane. After a reaction time of 2 h at approx. 85° C., 220 mliso-octane are added to separate off the aluminium complex formed andthe resulting product solution is admixed with 0.016 mol of urea and0.008 mol of water. The mixture is stirred for 1 h and the solid presentis filtered off at room temperature. After taking off the solvent invacuum, a melt remains which, after it is poured out, solidifies as apale-yellowish transparent glass.

PREPARATION EXAMPLE 6

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert.butylphenol, 102 ml pyridine in 220ml iso-octane. After a reaction time of 2 h at approx. 85° C., 220 mliso-octane are added to separate off the aluminium complex formed andthe resulting product solution is admixed with 0.045 mol of urea. Themixture is stirred for 1 h and the solid present is filtered off at roomtemperature. After taking off the solvent in vacuum, a melt remainswhich, after it is poured out, solidifies as a pale-yellowishtransparent glass.

PREPARATION EXAMPLE 7

The Friedel-Crafts product of 0.16 mol of diphenyl, 0.42 mol ofaluminium chloride and 0.35 mol of phosphorus trichloride is added to asolution of 0.63 mol of 2,4-di-tert-butylphenol, 120 ml pyridine in 220ml isooctane. After a reaction time of 2 h at approx. 85° C., 220 mlisooctane are added to separate off the aluminium complex formed and theresulting product solution is admixed with 0.0065 mol of calcium oxideand 0.026 mol of water. The mixture is stirred for 1 h and the solidpresent is filtered off at room temperature. After taking off thesolvent in vacuum, a melt remains which, after it is poured out,solidifies as a pale-yellowish transparent glass.

For the use examples below, the comparison product used is aphosphonite, which is commercially available as Sandostab P-EPQ fromClariant Huningue S.A. and is prepared according to GB Patent 1372528,Example 12.

USE EXAMPLE A

Comparison of the Clear Solubilities

10% strength solutions of products 1 to 6 and of the comparison productare prepared by dissolving 10 g of each substance in 90 g of isooctane.The solutions of the products 1 to 6 prepared according to the inventionare colorless and transparent, while the solution of the comparisonproduct is opaque and a precipitate is deposited after standing for ashort time. As a result, the products of the invention are suitable inparticular for adding as homogeneous solutions, additives in homogeneouscoatings systems and their prepolymeric components as well as in generalfor use in transparent end products, such as coatings, powder coatings,polycarbonate, polystyrene, polyethylene terephthalate, polybutyleneterephthalate, polyvinyl chloride, polymethylmethacrylate or cyclicolefin copolymers (COC), i.e. any polymeric materials which are presentto a high degree in the amorphous state having only small crystallinecontents.

USE EXAMPLE B

Comparison of the Chloride Contents

The contents of chloride or hydrolysable chlorine are determined byargentometric titration with potentiometric end point determination of aproduct suspension in water. For the products 1 to 4 prepared accordingto the invention, significantly lower chloride contents are foundcompared with the comparison product:

Chloride Prod. Prod. Prod. Prod. Prod. Prod. Comparison content 1 2 3 45 6 product in % 0.08 0.07 0.17 0.19 0.15 0.29 0.86

This reduction in chloride content by up to an order of magnituderepresents a significant improvement over the prior art which can beachieved without a substantial increase in resources andcost-effectively.

USE EXAMPLE C

Comparison of the Aluminium Contents

The contents of aluminium are determined by the method AES/ICP. For theproducts 1 to 6 prepared according to the invention, significantly loweraluminium contents are found compared with the comparison product:

aluminium Prod. Prod. Prod. Prod. Prod. Prod. Comparison content 1 2 3 45 6 product in ppm 275 330 450 400 250 500 940

This reduction in aluminium content represents a significant improvementover the prior art which can be achieved without a substantial increasein resources and cost-effectively.

USE EXAMPLE D Test of Application

Sample preparation: In a mixer

100 parts of LLDPE (linear low density polyethylene, MitsubishiF-30FG-N) powder 0.07 part of sterically hindered phenol (Irganox 1076)and 0.075, 0.10 or 0.125 part of the relevant stabilizer

are mixed together in the dry state and homogenized in a Collinsingle-screw extruder initially at 210° C. and then, after granulation,in a Göttfert Extrusiometer (compression 1:3, 70 min⁻¹) extruded a totalof five times at 240° C. and granulated. After the first, third, andfifth passage, the melt flow index (MFI) is determined each time (Zwick,190° C., 2.16 kg). The results obtained are summarized below.

Comparison MFI [g/10 min] Conc. [phr] Product 1 Product 2 product 1^(st)passage 0.075 1.00 0.99 0.98 0.100 0.99 0.97 0.98 0.125 0.98 0.98 0.983^(rd) passage 0.075 0.93 0.94 0.91 0.100 0.97 0.99 0.99 0.125 0.99 0.990.98 5^(th) passage 0.075 0.74 0.76 0.70 0.100 0.93 0.97 0.87 0.125 0.940.97 0.82

The products 1 and 2 of the invention equally show an improvedstabilizing action compared with the comparison product, in particularwith high demands being placed on the stabilizer action, expressed by anMFI value which is as high (LLDPE is mainly degraded by cross-linking,leading to low MFI-values) and as unchanged as possible, especiallyafter the 5th extrusion passage.

USE EXAMPLE E

Test of Application

Sample preparation: In a mixer

100 parts of PP (polypropylene, Solvay Polyolefins Eltex P HL 001PF)powder

0.05 parts of sterically hindered phenol (Irganox1010) and

0.04 resp.

0.07 parts of the relevant stabilizer

are mixed together in the dry state and homogenized in a Collin singlescrew extruder initially at 210° C. and then, after granulation, in aGöttfert Extrusiometer (compression 1:3, 50 min³¹ ¹) extruded a total offive times at 270° C. and granulated. After the first, third and fifthpassage, the melt flow index (MFI) is determined each time (Zwick, 230°C., 2.16 kg). The results obtained are summarized below

MFI [/10 min], 0.04 parts of stabilizer Product 2 Product 7 Comparisonproduct 1^(st) passage 3.17 3.48 4.34 3^(rd) passage 4.61 5.83 8.805^(th) passage 7.22 10.20 15.10 MFI [/10 min], 0.07 parts of stabilizerProduct 2 Product 7 Comparison product 1^(st) passage 2.58 2.75 2.813^(rd) passage 2.80 3.72 4.15 5^(th) passage 3.76 4.62 6.11

The products 2 and 7 equally show improved stabilizing action comparedto the comparison product, in particular with high demands being placedon the stabilizer action, expressed by an MFI-value which is as low (PPis degraded by chain scission, leading to high MFI-values) and asunchanged as possible, especially after the 5^(th) extrusion passage.

The stabilizing effect is found to be concentration-independent, i.e.not limited to a small concentration range and the results show that thestabilizers prepared according to the invention have a markedly improvedspecific stabilizing action in various polymers compared with the priorart (Comparison Product).

What is claimed is:
 1. A phosphonite or phosphinite of general formula(I)

where aryl is a substituted or unsubstituted aryl or heteroaryl radical;R is any organic radical having 5-36 carbon atoms, which can alsocontain hetero atoms; and A is either R or OR, prepared by reacting aFriedel-Crafts reaction product of general formula (II)

where aryl has the meaning above; Hal is halogen; and A′ is either Halor R, with a hydroxyl compound of the formula (III) R—OH  (III) where Rhas the meaning above, separating off a majority of insoluble byproductsformed during the reaction, characterized in that an aftertreatment iscarried out wherein the aftertreatment comprises: adding a) a proticcompound selected from the group consisting of alcohols, ammonia,primary amines, secondary amines and water, or b) an oxide, hydroxide,(hydrogen)carbonate or (hydrogen)phosphate of a metal, or c) a nitrogencontaining compound selected from the group consisting of carbonic acidamides, thiocarbonic acid amides, carbonic acid imides, thiocarbonicacid imides, lactames, thiolactames, carbonic acid hydrazides, urea,thiourea, symmetrically and asymmetrically substituted urea and thioureaderivatives, urethanes, uretimides, guanidine and its salts and melamineand derivatives thereof, including polymeric compounds of all namedclasses, or d) any combination of one or more of the compounds of a) toc), wherein the addition of a) to d) is carried out in the absence of asolvent or in an inert, nonpolar solvent, and separating off resultingbyproducts from the reaction mixture, wherein the phosphonite orphosphinite is characterized by a content of chloride or hydrolysablechlorine, determined by argentometric titration, of less than 0.5%.
 2. Aphosphonite or phosphinite of general formula (I)

where aryl is a substituted or unsubstituted aryl or heteroaryl radical;R is any organic radical having 5-36 carbon atoms, which can alsocontain hetero, atoms; and A is either R or OR, prepared by reacting aFriedel-Crafts reaction product of general formula (II)

where aryl has the meaning above; Hal is halogen; and A′ is either Halor R, with a hydroxyl compound of the formula (III) R—OH  (III) where Rhas the meaning above, separating off a majority of insoluble byproductsformed during the reaction, characterized in that an aftertreatment iscarried out wherein the aftertreatment comprises: adding a) a proticcompound selected from the group consisting of alcohols, ammonia,primary amines, secondary amines and water, or b) an oxide, hydroxide,(hydrogen)carbonate or (hydrogen)phosphate of a metal, or c) a nitrogencontaining compound selected from the group consisting of carbonic acidamides, thiocarbonic acid amides, carbonic acid imides, thiocarbonicacid imides, lactames, thiolactames, carbonic acid hydrazides, urea,thiourea, symmetrically and asymmetrically substituted urea and thioureaderivatives, urethanes, uretimides, guanidine and its salts and melamineand derivatives thereof, including polymeric compounds of all namedclasses, or d) any combination of one or more of the compounds of a) toc), wherein the addition of a) to d) is carried out in the absence of asolvent or in an inert, nonpolar solvent, and separating off resultingbyproducts from the reaction mixture, wherein the phosphonite orphosphinite is characterized by an aluminium content less than 500 ppm,determined by the AES/ICP method.
 3. The phosphonite according to claim1 which is a reaction product of 2,4-di-tert-butylphenol with theFriedel-Crafts reaction product of diphenyl and phosphorus trichloride.4. The phosphonite according to claim 2, which is a reaction product of2,4-di-tert-butylphenol with the Friedel-Crafts reaction product ofdiphenyl and phosphorus trichloride.